Heterointerface Engineering-Induced Oxygen Defects for the Manganese Dissolution Inhibition in Aqueous Zinc Ion Batteries

Manganese-based material is a prospective cathode material for aqueous zinc ion batteries(ZIBs)by virtue of its high theoretical capacity,high operating voltage,and low price.However,the manganese dissolution during the electrochemical reaction causes its electrochemical cycling stability to be undesirable.In this work,heterointerface engineering-induced oxygen defects are introduced into heterostructure MnO_(2)(δa-MnO_(2))by in situ electrochemical activation to inhibit manganese dissolution for aqueous zinc ion batteries.Meanwhile,the heterointerface between the disordered amorphous and the crystalline MnO_(2)ofδa-MnO_(2)is decisive for the formation of oxygen defects.And the experimental results indicate that the manganese dissolution ofδa-MnO_(2)is considerably inhibited during the charge/discharge cycle.Theoretical analysis indicates that the oxygen defect regulates the electronic and band structure and the Mn-O bonding state of the electrode material,thereby promoting electron transport kinetics as well as inhibiting Mn dissolution.Consequently,the capacity ofδa-MnO_(2)does not degrade after 100 cycles at a current density of 0.5 Ag^(-1)and also 91%capacity retention after 500cycles at 1 Ag^(-1).This study provides a promising insight into the development of high-performance manganese-based cathode materials through a facile and low-cost strategy.

Facile synthesis of Cu-doped manganese oxide octahedral molecular sieve for the efficient degradation of sulfamethoxazole via peroxymonosulfate activation

Advanced processes for peroxymonosulfate(PMS)-based oxidation are efficient in eliminating toxic and refractory organic pol-lutants from sewage.The activation of electron-withdrawing HSO_(5)^(-)releases reactive species,including sulfate radical(·SO_(4)^(-)),hydroxyl radical(·OH),superoxide radical(·O_(2)^(-)),and singlet oxygen(1O_(2)),which can induce the degradation of organic contaminants.In this work,we synthesized a variety of M-OMS-2 nanorods(M=Co,Ni,Cu,Fe)by doping Co^(2+),Ni^(2+),Cu^(2+),or Fe^(3+)into manganese oxide oc-tahedral molecular sieve(OMS-2)to efficiently remove sulfamethoxazole(SMX)via PMS activation.The catalytic performance of M-OMS-2 in SMX elimination via PMS activation was assessed.The nanorods obtained in decreasing order of SMX removal rate were Cu-OMS-2(96.40%),Co-OMS-2(88.00%),Ni-OMS-2(87.20%),Fe-OMS-2(35.00%),and OMS-2(33.50%).Then,the kinetics and struc-ture-activity relationship of the M-OMS-2 nanorods during the elimination of SMX were investigated.The feasible mechanism underly-ing SMX degradation by the Cu-OMS-2/PMS system was further investigated with a quenching experiment,high-resolution mass spec-troscopy,and electron paramagnetic resonance.Results showed that SMX degradation efficiency was enhanced in seawater and tap water,demonstrating the potential application of Cu-OMS-2/PMS system in sewage treatment.

Covalency competition induced selective bond breakage and surface reconstruction in manganese cobaltite towards enhanced electrochemical charge storage

Manganese cobaltite(MnCo_(2)_(4))is a promising electrode material because of its attractive redox chemistry and excellent charge storage capability.Our previous work demonstrated that the octahedrally-coordinated Mn are prone to react with the hydroxyl ions in alkaline electrolyte upon electrochemical cycling and separates on the surface of spinel to reconstruct into d-MnO_(2) nanosheets irreversibly,thus results in a change of the reaction mechanism with Kþion intercalation.However,the low capacity has greatly limited its practical application.Herein,we found that the tetrahedrally-coordinated Co_(2) þions were leached when MnCo_(2)_(4) was equilibrated in 1 mol L^(-1) HCl solution,leading to the formation of layered CoOOH on MnCo_(2)_(4) surface which is originated from the covalency competition induced selective breakage of the CoT–O bond in CoT–O–CoO and subsequent rearrangement of free Co_(6) octahedra.The as-formed CoOOH is stable upon cycling in alkaline electrolyte,exhibits conversion reaction mechanism with facile proton diffusion and is free of massive structural evolution,thus enables utilization of the bulk electrode material and realizes enhanced specific capacity as well as facilitated charge transfer and ion diffusion.In general,our work not only offers a feasible approach to deliberate modification of MnCo_(2)_(4)'s surface structure,but also provides an in-depth understanding of its charge storage mechanism,which enables rational design of the spinel oxides with promising charge storage properties.

Catalysis of Manganese(II) on Chromium(VI) Reduction by Citrate

The catalysis of manganese（Ⅱ） （Mn^2＋） on chromium（Ⅵ） （Cr^6＋） reduction by citrate was studied through batch experiments with the concentration of citrate greatly in excess of Cr^6＋ at 25 ℃ and in pH ranges of 4.0 go 5.0. Results showed that at pH 4.5 within 22 h direct reduction of Cr^6＋ by citrate was not observed, bug for the same time when Mn^2＋ （50 to 200 μmol L^-1） was added, nearly all Cr^6＋ was reduced, with the higher initial Mn^2＋ concentration having faster Cr^6＋ reduction. In the initial stage of the reaction, the Cr^6＋ reduction could be described with a pseudo-first-order kinetics equation. In the lager stage of the reaction, plots of lnc（Cr^6＋） versus t, where c（Cr^6＋） is the Cr^6＋ concentration in the reaction and t is the reaction time, deviated from the initial linear trend. The deviations suggested that the pseudo-first-order kinetics did not apply go the whole experimental period and that some reaction intermediates could have greatly accelerated Cr^6＋ reduction by citrate. The catalysis of the intermediates increased with the reaction time and gradually reached stability. Then, the plot of lnc（Cr^6＋） versus t in the presence of Mn^2＋ was linear again, with the rate constant increasing by 102 times compared with the absence of Mn^2＋. Complexation between Mn^2＋ and citrate was likely a prerequisite for the catalysis of Mn^2＋ on the reaction. Additional experiments showed that introducing eghylenediaminegegraacegic acid （EDTA） into the reaction system strongly suppressed the catalysis of Mn^2＋.

Hydrothermal Synthesis and Crystal Structure of a New Manganese(II) Complex with 2,4-Pyridine-dicarboxylic Acid and 2,2′-Bipyridine Ligands

A new metal-organic complex [Mn2（PDC）2（bipy）2（H2O）2] （H2PDC = 2,4-pyridine-dicarboxylic acid, bipy = 2,2′-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The compound crystallizes in triclinic, space group P ^-1 with a = 7.376（3）, b = 9.990（4）, c = 11.950（5） A^°, α= 75.217（5）, β = 78.052（5）, γ = 70.655（5）°, V = 796.0（5）A^°3, C34HE6Mn2N6O10, Mr = 788.49, De = 1.645 g/cm^3,μ（MoKa） = 0.866 mm^-1, F（000） = 235, Z = 1, the final R = 0.0425 and wR = 0.0700 for 1971 observed reflections （I 〉 2σ（I））. In the crystal structure, the manganese atom is six-coordinated by two carboxylate oxygen atoms from two different PDC ligands, one aqua ligand, and three nitrogen atoms from 2,2′-bipy and PDC ligands, giving a distorted octahedral geometry. It exhibits a three-dimensional supramolecular network defined by O-H…O hydrogen-bonding interactions.

Synthesis and Crystal Structure of a One-dimensional Azido-bridged Manganese (II) Compound [Mn(N_3)_2(H_2O)_3·C_6H_(12)N_4]_n

A new one-dimensional azido-bridged manganese compound has been prepared and structurally characterized by X-ray diffraction. The complex [Mn（N3）2（H2O）3·C6H12N4]n crystallizes in space group Pnma with a = 6.5252 （5）, b = 9.3226（7）, c = 22.2070（15） ,A°, V= 1350.89（17） ,A°^3, Z = 4, Mr = 333.24, Dc = 1.639 g/cm^3, μ = 1.005 mm^-1 and F（000） = 692. The final refinement gave R = 0.0328 and wR = 0.0777 for 1085 observed reflections with I 〉 2σ（I）. The structure contains [Mn（N3）2（H2O）3]n polymeric chains and uncoordinated hexamethylenetetramine （HMTA） molecules with Mn/HMTA molar ratio of 1：1. The Mn atoms are bridged by end-to-end azido ligands to construct one-dimensional zig-zag infinite chains. Each Mn atom is six-coordinated by three N atoms of three azido ligands and three water O atoms, resulting in an octahedral geometry. Extending hydrogenbonding interactions involving water O atoms, azido and HMTA N atoms link the chains and HMTA molecules into a three-dimensional network.

Dietary manganese supplementation inhibits abdominal fat deposition possibly by regulating gene expression and enzyme activity involved in lipid metabolism in the abdominal fat of broilers

Excessive abdominal fat deposition seriously restricts the production efficiency of broilers.Several studies found that dietary supplemental manganese(Mn)could effectively reduce the abdominal fat deposition of broilers,but the underlying mechanisms remain unclear.The present study aimed to investigate the effect of dietary supplementation with the inorganic or organic Mn on abdominal fat deposition,and enzyme activity and gene expression involved in lipid metabolism in the abdominal fat of male or female broilers.A total of 4201-d-old AA broilers(half males and half females)were randomly allotted by body weight and gender to 1 of 6 treatments with 10 replicates cages of 7 chicks per cage in a completely randomized design involving a 3(dietary Mn addition)×2(gender)factorial arrangement.Male or female broilers were fed with the Mn-unsupplemented basal diets containing 17.52 mg Mn kg^(-1)(d 1-21)and 15.62 mg Mn kg^(-1)(d 22-42)by analysis or the basal diets supplemented with 110 mg Mn kg^(-1)(d 1-21)and 80 mg Mn kg^(-1)(d 22-42)as either the Mn sulfate or the Mn proteinate with moderate chelation strength(Mn-Prot M)for 42 d.The results showed that the interaction between dietary Mn addition and gender had no impact(P>0.05)on any of the measured parameters;abdominal fat percentage of broilers was decreased(P<0.003)by Mn addition;Mn addition increased(P<0.004)adipose triglyceride lipase(ATGL)activity,while Mn-Prot M decreased(P<0.002)the fatty acid synthase(FAS)activity in the abdominal fat of broilers compared to the control;Mn addition decreased(P<0.009)diacylglycerol acyltransferase 2(DGAT2)mRNA expression level and peroxisome proliferator-activated receptor γ(PPARγ)mRNA and protein expression levels,but up-regulated(P<0.05)the ATGL mRNA and protein expression levels in the abdominal fat of broilers.It was concluded that dietary supplementation with Mn inhibited the abdominal fat deposition of broilers possibly via decreasing the expression of PPARγand DGAT2 as well as increasing the expression and activity of ATGL in the abdominal fat of broilers,and Mn-Prot M was more effective in inhibiting the FAS acitivity.

Catagenetic type of manganese ores:REE and isotope(δ^(13)C,δ^(18)O)geochemical features(on the example of the Usa deposit,Russia)

Chemical(REE and major elements)and isotope(δ^(13)C,δ^(18)O)composition of carbonate manganese ores and manganese-bearing carbonates of the Usa deposit(Siberia,Russia)were studied.Received data on the composition of REE exhibit both the distinct negative(Ce/Ce*_(PAAS)<1)and positive(Ce/Ce*_(PAAS)>1)cerium anomalies and the positive Eu-anomaly(Eu/Eu*_(PAAS)>1).Negative Eu-anomalies are not observed.The contents of Mn,Fe,REE,and Ce-anomalies show a positive correlation with each other.Ce-anomalies and the amount of manganese and REE in relation to the carbon isotope composition(δ^(13)C)show a negative relationship and indicate that oxidized carbon of organic matter played an important role in the concentration of manganese and REE in manganese ores.The chemical and isotope composition of examined rocks indicates on secondary formation of Mnores.Two major phases and sources are distinguished in the ore-forming process characterized by diff erent chemical(REE and ore elements)and isotope composition:(i)highgrade manganese ores(with high contents of REE and light carbon isotope composition)and(ii)low-grade manganese ores(with low contents of REE and heavy carbon isotope composition).

Synergism of preintercalated manganese ions and lattice water in vanadium oxide cathodes for high-capacity and long-life Zn-ion batteries

Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials.In this work,we present an intercalation mechanism-based cathode materials for AZIB,i.e.the vanadium oxide with pre-intercalated manganese ions and lattice water(noted as MVOH).The synergistic effect between Mn^(2+)and lattice H_(2)O not only expands the interlayer spacing,but also significantly enhances the structural stability.Systematic in-situ and ex-situ characterizations clarify the Zn^(2+)/H^(+)co–(de)intercalation mechanism of MVOH in aqueous electrolyte.The demonstrated remarkable structure stability,excellent kinetic behaviors and ion-storage mechanism together enable the MVOH to demonstrate satisfactory specific capacity of 450 mA h g^(−1)at 0.2 A g^(−1),excellent rate performance of 288.8 mA h g^(−1)at 10 A g^(−1)and long cycle life over 20,000 cycles at 5 A g^(−1).This work provides a practical cathode material,and contributes to the understanding of the ion-intercalation mechanism and structural evolution of the vanadium-based cathode for AZIBs.

Hydrothermal Synthesis and Crystal Structure of a Manganese(II) Coordination Polymer with 1,1′-Biphenyl-2,2′,6,6′-tetracarboxyl Acid and 2,2′:6,2′′-Terpyridine Ligands

The title compound {[Mn（H2BPTC）（tpy）（H2O）]·（H2O）3}, （1, H4BPTC = 1,1＇- biphenyl-2,2＇,6,6＇-tetracarboxylic acid, tby = 2,2＇：6,2＇-terpyridine） has been synthesized by the hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of monoclinic, space group P21/c with a = 10.971（2）, b = 20.776（4）, c = 14.332（3） A, β = 109.25（3）°, MnC31H27N3O12, Mr = 688.50, V= 3084.1（10） A^3, Dc = 1.483 g/cm^3, F（000） = 1420, p = 0.498 mm^-1, S = 1.066 and Z = 4. The final refinement gave R = 0.0447 and wR = 0.1103 for 5107 observed reflections with I 〉 2σ（I）. The title complex has a {[Mn（H2BPTC）（tpy）（H2O）]}, chain structure, and the hydrogen bonding interactions make it more stable. Each chain is further connected to the adjacent ones through π…π, C-H…π and rich hydrogen bonds to form a metal-organic coordination polymer.

Preparation of Manganese Oxide and Its Adsorption Properties

The in-situ oxidation of manganese sulfate solution with H2O_(2),sodium hypochlorite,potassium permanganate and oxygen as oxidants was investigated by means of SEM,EDS,XRD,BET and infrared analysis,and the effects of different oxidants on the morphology,phase composition,surface properties and specific surface area of manganese oxides were investigated.The experimental results show that the diameter of manganese oxide particles prepared with H_(2)O_(2)is the smallest,about 50 nm,and the specific surface area is the largest,63.8764 m^(2)/g.It has the advantages of abundant surface hydroxyl groups,no introduction of other impurities and large adsorption potential.It is most suitable to be used as an oxidant for oxidizing manganese sulfate solution to prepare manganese oxide by in-situ oxidation.Nano manganese oxide prepard by H_(2)O_(2)in-situ oxidation method is used as adsorbent to adsorb cobalt and nickel impurities in manganese sulfate.When the reaction pH is 6,the reaction time is 30min and the amount of adsorbent is 1.0 g,the adsorption rates of cobalt and nickel impurities in 100ml manganese sulfate solution are 97.59%and 97.67%,respectively.The residual amounts of cobalt and nickel meet the industrial process standard of first-class products(Co,Ni w/%≤0.005)of high-purity manganese sulfate(Hg/t4823-2015)for batteries.The study plays a guiding role in the preparation and regulation of manganese oxide,and provides a new method with high efficiency,purity and adsorbent availability for the preparation of high-purity manganese sulfate solution.

Interfacial engineering of manganese-based oxides for aqueous zinc-ion batteries: Advances, mechanisms, challenges and perspectives

Manganese(Mn)-based materials are considered as one of the most promising cathodes in zinc-ion batteries(ZIBs) for large-scale energy storage applications because of their multivalence, cost-effectiveness,natural availability, low toxicity, satisfactory capacity, and high operating voltage. In this review, the research status and related interface engineering strategies of Mn-based oxide cathode electrode materials for ZIB in recent years are summarized. Specifically, the review will focus on three types of interface engineering strategies, including interface reconstruction via cathode, interface reconstruction electrolyte, and protection via artificial cathode-electrolyte interphase(CEI) layer, within the context of their evolution of interface layer and corresponding electrochemical performance. A series of experimental variables, such as crystal structure, electrochemical reaction mechanism, and the necessary connection for the formation and evolution of interface layer, will be carefully analyzed by combining various advanced characterization techniques and theoretical calculations. Finally, suggestions and strategies are provided for reasonably designing the cathode-electrolyte interface to realize the excellent performance of Mn-based oxide zinc-based batteries.

Enhanced recovery of high-purity Fe powder from iron-rich electrolytic manganese residue by slurry electrolysis

Iron-rich electrolytic manganese residue(IREMR)is an industrial waste produced during the processing of electrolytic metal manganese,and it contains certain amounts of Fe and Mn resources and other heavy metals.In this study,the slurry electrolysis technique was used to recover high-purity Fe powder from IREMR.The effects of IREMR and H2SO4 mass ratio,current density,reaction temper-ature,and electrolytic time on the leaching and current efficiencies of Fe were studied.According to the results,high-purity Fe powder can be recovered from the cathode plate,and the slurry electrolyte can be recycled.The leaching efficiency,current efficiency,and purity of Fe reached 92.58%,80.65%,and 98.72wt%,respectively,at a 1:2.5 mass ratio of H2SO4 and IREMR,reaction temperature of 60℃,electric current density of 30 mA/cm^(2),and reaction time of 8 h.In addition,vibrating sample magnetometer(VSM)analysis showed that the coercivity of electrolytic iron powder was 54.5 A/m,which reached the advanced magnetic grade of electrical pure-iron powder(DT4A coercivity standard).The slurry electrolytic method provides fundamental support for the industrial application of Fe resource recovery in IRMER.

pH-Dependence of Manganese (II) Oxidation Reaction by Novel Wild-Type and Mutants Recombinant Phlebia radiata Manganese Peroxidase 3 (rPr-MnP3) Enzymes

The goal of this study was to determine whether mutation of the Mn-binding site of wild-type recombinant Phlebia radiata manganese peroxidase 3 affected the pH-dependence kinetic parameters. pH range investigated was 2.5 – 12.0. The catalytic efficiency of the mutant enzymes at high and low pH in comparison to the wild-type was investigated using standard rPr-MnP3 protocol. Wild-type recombinant Phlebia radiata MnP3 enzyme showed optimal activity with Mn (II) as substrate at pH 5.0 and remained moderately active (approximately 40%) in the pH range of 6.0 - 9.0. The rPr-MnP3 mutants’ maximum activity ranged between 5.5 and 8.0. Wild-type and mutants rPr-MnP3 enzymes exhibited a similar pH profile with optimum pH of 3.0 for ABTS oxidation. Mutation has severely decreased the catalytic efficiency for Mn (II) oxidation at pH 5.0. The rPr-MnP3 enzymes showed enhanced affinity for Mn (II) at alkaline pH and a more alkaline range for catalysis than ever reported for any Manganese Peroxidase. This study reveals that at higher pH, rPr-MnP3 can function with alternative ligands in the Mn (II) site and does not have an absolutely obligate requirement for an all carboxylate ligand set. These results further strongly confirm that Mn2+ binding site is the only productive catalytic site for Mn (II) oxidation.

Synthesis and Crystal Structure of Tetrakis(1-vinylimidazole-kN^3)diisothiocyanatomanganese(II)

The title compound I （C22H24MnN10S2, Mr = 547.57） has been synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group P2 1/c with a = 8.6010（17）, b = 9.0180（18）, c = 17.773（4）A, β = 101.79（3）°, V = 1349.5（5）A^3, Z = 2, Dc = 1.348 g/cm^3,/1 = 0.674 mm^-1, F（000） = 566, the final R = 0.0488 and wR = 0.1289. In the structure, each Mn atom is coordinated by four Vim （Vim = 1-vinylimidazole） ligands and a pair of monodentate isothioeyanic groups, affording a compressed oetahedral MnN6 core.

The Influence of CO_(2) Cured Manganese Slag on the Performance and Mechanical Properties of Ultra-High Performance Concrete

The presence of toxic elements in manganese slag(MSG)poses a threat to the environment due to potential pollution.Utilizing CO_(2) curing on MS offers a promising approach to immobilize toxic substances within this material,thereby mitigating their release into the natural surroundings.This study investigates the impact of CO_(2) cured MS on various rheological parameters,including slump flow,plastic viscosity(η),and yield shear stress(τ).Additionally,it assesses flexural and compressive strengths(f_(t) and f_(cu)),drying shrinkage rates(DSR),durability indicators(chloride ion migration coefficient(CMC),carbonization depth(CD)),and the leaching behavior of heavy metal elements.Microscopic examination via scanning electron microscopy(SEM)is employed to elucidate the underlying mechanisms.The results indicate that CO_(2) curing significantly enhances the slump flow of ultra-high performance concrete(UHPC)by up to 51.2%.Moreover,it reduces UHPC’sηandτby rates ranging from 0%to 52.7%and 0%to 40.2%,respectively.The DSR exhibits a linear increase corresponding to the mass ratio of CO_(2) cured MS.Furthermore,CO_(2) curing enhances both f_(t) and f_(cu) of UHPC by up to 28.7%and 17.6%,respectively.The electrical resistance is also improved,showing an increase of up to 53.7%.The relationship between mechanical strengths and electrical resistance follows a cubic relationship.The CO_(2) cured MS demonstrates a notable decrease in the CMC and CD by rates ranging from 0%to 52.6%and 0%to 26.1%,respectively.The reductions of leached chromium(Cr)and manganese(Mn)are up to 576.3%and 1312.7%,respectively.Overall,CO_(2) curing also enhances the compactness of UHPC,thereby demonstrating its potential to improve both mechanical and durability properties.

Understanding the roles of Brønsted/Lewis acid sites on manganese oxide-zeolite hybrid catalysts for low-temperature NH_(3)-SCR

Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NO_(x)removal reactions through the inter-particle diffusion of intermediate species,their subsequent reaction mechanism on acid sites is still unclear and requires investigation.In this study,the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions,which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species.Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NO_(x)with NH_(3)(NH_(3)-SCR)reaction demonstrate that the Lewis acid sites over MnO_(x)are more active for NO reduction but have lower selectivity to N_(2)than Brønsted acids sites.Brønsted acid sites primarily produce N_(2),whereas Lewis acid sites primarily produce N_(2)O,contributing to unfavorable N_(2)selectivity.The Brønsted acid sites present in Y zeolite,which are stronger than those on MnO_(x),accelerate the NH_(3)-SCR reaction in which the nitrite/nitrate species diffused from the MnO_(x)particles rapidly convert into the N_(2).Therefore,it is important to design the catalyst so that the activated NO species formed in MnO_(x)diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnO_(x)particle.For the physically mixed H-MnO_(x)+H-Y sample,the abundant Brønsted/Lewis acid sites in H-MnO_(x)give rise to significant consumption of activated NO species before their inter-particle diffusion,thereby hindering the enhancement of the synergistic effects.Furthermore,we found that the intercalated K+in K-MnO_(x)has an unexpected favorable role in the NO reduction rate,probably owing to faster diffusion of the activated NO species on K-MnO_(x)than H-MnO_(x).This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.

Synthesis and Crystal Structure of a Novel Tetranuclear Manganese(II) Complex with a Tripodal Peptide Ligand

The title complex, [Mn2(O-Py3A)(DPK-CH3O)(CH3OH)]2?2ClO4?4CH3OH (C64H70Cl2- Mn4N12O22, Py3AH = N-(bis(2?-pyridyl)methyl)-2-pyridinecarboxamide, DPK = di-2-pyridyl ketone) has been synthesized and its crystal structure was determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 12.667(9), b = 16.793(12), c = 17.070(13) ?, β = 100.997(13)o, V = 3565(5) ?3, Dc = 1.537 g/cm3, Mr = 1649.98, Z = 2, μ(MoKα) = 0.851 mm-1 and F(000) = 1696. The final R and wR are 0.0639 and 0.1320, respectively for 3979 observed reflec- tions with I > 2σ(I). In the tetranuclear complex, each Mn(II) atom is six-coordinated and the four Mn(II) atoms are coplanar, exhibiting a parallelogram arrangement; while the deprotonated ligands are oxidized to O-Py3A2- anions and cleaved to DPK-CH3O– anions (the monoanion of mono- methylated diol of DPK) furthermore.

Synthesis, Crystal Structure and Thermal Property of a Manganese(II) 4-Carboxyphenoxyacetate Complex

The manganese(II) complex, [Mn(phen)2(4-CPOA)(H2O)]?5H2O (4-CPOAH2 = 4- carboxyphenoxyacetic acid) has been synthesized and characterized by elemental analyses, IR, TG and single-crystal X-ray diffraction. The crystal is of monoclinic, space group C2/c, with a = 27.471(3), b = 18.490(4), c = 14.507(3) ?, β = 115.13(3)o, V = 6671(3) ?3, Z = 8, Mr = 717.58, Dc= 1.429 g/cm3, μ = 0.462 mm–1, F(000) = 2984, the final R = 0.0535 and wR = 0.1200 for 5413 observed reflections with I > 2σ(I). The Mn(II) atom is coordinated by one O atom of 4-carboxy- phenoxyacetate, four N atoms of two 1,10-phenanthroline and one water molecule, residing in a distorted octahedral environment. A supramolecular network structure is formed by hydrogen bonds and π-π stacking interactions.

Preparation, Characterization, and Application of Manganese Oxide Coated Zeolite as Adsorbent for Removal of Copper(II) Ions from Seawater

The present study is aimed to examine the adsorption characteristics of Cu(II) by using the novel cellulose acetate composite and to apply it for the removal of Cu(II) from real wastewater samples. In order to achieve this objective, ethylenediamine, diethylenetriamine, triethylenetetramine and te-traethylenepentanene were used for immobilization of grafted cellulose acetate-nanoscale manganese dioxide. Cellulose was extracted from mangrove species Avicennia marina and converted to cellulose acetate then it was formed composite with nano-manganese dioxide via precipitation of nano-manganese dioxide on it. The composite was grafted with acrylamide monomer before immobilization. The synthesized compounds were used for adsorption of Cu(II) and characterized by FT-IR, TGA and SEM. The adsorption characteristics of synthesized sorbents were optimized. Langmuir and Freundlich models were used to establish sorption equilibria. The analytical applications of these modified materials were applied successfully for the removal of Cu(II).